Laser-induced breakdown spectroscopy (LIBS) has been applied to the direct analysis of powdered tungsten carbide hard-metal precursors and cemented tungsten carbides. The aim of this work was to examine the possibility of quantitative determination of the niobium, titanium, tantalum and cobalt. The investigated samples were in the form of pellets, pressed with and without binder (powdered silver) and in the form of cemented tungsten carbides. The pellets were prepared by pressing the powdered material in a hydraulic press. Cemented tungsten carbides were embedded in resin for easier manipulation.
Several lasers and detection systems were utilized. The Nd:YAG laser working at a basic wavelength of 1064 nm and fourth-harmonic frequency of 266 nm with a gated photomultiplier or ICCD detector HORIBA JY was used for the determination of niobium which was chosen as a model element. Different types of surrounding gases (air, He, Ar) were investigated for analysis. The ICCD detector DICAM PRO with Mechelle 7500 spectrometer with ArF laser (193 nm) and KrF laser (248 nm) were employed for the determination of niobium, titanium, tantalum and cobalt in samples under air atmosphere. Good calibration curves were obtained for Nb, Ti, and Ta (coefficients of determination r2 > 0.96). Acceptable calibration curves were acquired for the determination of cobalt (coefficient of determination r2 = 0.7994) but only for the cemented samples. In the case of powdered carbide precursors, the calibration for cobalt was found to be problematic. 相似文献
[Mg(HF)2](SbF6)2 and [Ca(HF)2](SbF6)2 monocrystals were grown from the corresponding hexafluoroantimonates(V) dissolved in anhydrous hydrogen fluoride. [Mg(HF)2](SbF6)2 crystallizes in the space group Pnma (no. 62) with a=1249.1(4) pm, b=1230.2(4) pm, c=699.1(2) pm, V=1.0742(6) nm3, Z=4. Magnesium is octahedrally coordinated by six fluorine atoms from which two belong to two HF molecules. The structure can be represented by alternating rows of magnesium and antimony atoms running parallel to the c-axis. Magnesium atoms are connected by cis bridging Sb(2)F6 units along the a-axis and by trans bridging Sb(1)F6 units along the b-axis. In this way a three-dimensional network is formed.[Ca(HF)2](SbF6)2 crystallizes in the space group P21/n (no. 14) with a=935.2(3) pm, b=1088.7(3) pm, c=1104.8(3) pm, β=106.697(5)°, V=1.0774(5) nm3, Z=4. The coordination sphere around the calcium atom consists of eight fluorine atoms which define the vertices of an Archimedean antiprism. The two HF molecules directly coordinate the calcium atom and their fluorine atoms are placed in the corners of different square faces of the Archimedean antiprism. The Ca-F(HF) distances are shorter than the Ca-F(Sb) distances. The Sb(1)F6 and Sb(2)F6 groups have four equatorial bridging fluorine atoms, while the Sb(3)F6 groups have only two bridging trans F ligands. The Ca atoms in the [−1,0,1] plane are connected by equatorial F ligands of Sb(1)F6 and Sb(2)F6 units, forming a [Ca(SbF6)+]n layer. These layers are connected by trans bridging Sb(3)F6 groups. HF molecules occupy the space between these layers and additionally contribute to the connection between the layers by hydrogen bonding. 相似文献
A novel and simple flow-based method was developed for the simultaneous determination of As(III) and As(V) in freshwater samples. Two miniature columns with a solid phase anion exchange resin, placed on two 6-way valves were utilized for the solid-phase collection/concentration of arsenic(III) and arsenic(V), respectively. As(III) could be retained on the column after its oxidation to As(V) species with an oxidizing agent. The collected analytes were then sequentially eluted by 2 M nitric acid and introduced into ICP-AES. Potassium permanganate was examined as potential oxidizing agent for conversion of As(III) to As(V). The standard deviation of the analytical signals (peak height) for the replicate analysis (n = 5) of 0.5 μg l−1 solution were 3 and 5% for As(III) and As(V), respectively. The limit of detection (3σ) for both As(III) and As(V) were 0.1 μg l−1. The proposed system produced satisfactory results on the application to the direct analysis of inorganic arsenic species in freshwater samples. 相似文献
Complexation of Ni(II), Cu(II), Zn(II), and Cd(II) by dissolved organic carbon (DOC) in some freshwater lakes in Rouyn-Noranda, Québec, Canada, where they were impacted by effluents from a nearby copper smelter, was measured by kinetic and equilibrium methods using cathodic and anodic stripping voltammetry. The measured free-metal-ion and labile metal-complex concentrations were compared with the predictions made by a widely-used computer speciation model, the Windermere Humic Aqueous Model (WHAM): WHAM V and its improved version WHAM VI. If it is assumed that 65% of the DOC is “active”, i.e. behaving as isolated humic substances such as fulvic acid, both versions of WHAM are able to predict the labile and free-metal-ion concentrations of Ni, Zn, and Cd reasonably well; however, both underestimate the free-copper-ion concentration by one to two orders of magnitude. WHAM VI is generally better than or equal to WHAM V for successfully predicting most of the free-metal-ion concentrations. The modelled competition by Al(III) and Fe(III) in the lake surface waters showed that in most cases Cu(II) was most affected by this competition. WHAM VI predicts a larger effect from the Al(III) and Fe(III) competition than does WHAM V. 相似文献
A new class of coordination compounds of the type [Mn+(L)p](AF6−)n and [Mn+(L)r](BF4−)n, where M is Mg, Ca, Sr, Ba, Cd, Pb, lanthanides, A is P, As, Sb, Bi and L is XeF2, XeF4, XeF6, KrF2, was studied. A review of all known coordination compounds with L is XeF2 is given: (a) synthetic routes for the preparation of these compounds; (b) analysis of their crystal structures (molecular, dimer, chain, double chain, layer, strongly interconnected double layers and three-dimensional network); (c) the influence of the ligand XeF2 (small formula volume, linear, semi-ionic, charge of −0.5e on each F ligand); (d) the influence of the central metal ion; (e) the influence of the anions: AF6− and BF4− (the formula volume, Lewis basicity). On the basis of all properties of the metal ions, ligand and anions the obtained variety of the structures is analyzed. 相似文献
Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme. 相似文献